Alicyclic bifunctional compounds and processes for their preparation

ABSTRACT

The invention provides an alicyclic bifunctional compound represented by the formula ##STR1## wherein R is a carboxyl group, a lower alkoxycarbonyl group or a hydroxymethyl group and n is 0 or 1.

The present invention relates to novel alicyclic compounds and processesfor preparing the compounds. The invention more particularly concernswith alicyclic bifunctional compounds useful as materials forpolyesters, polycarbonates, etc. and with processes for theirpreparation.

Polyesters prepared from monomers having an alicyclic skeleton such asalicyclic dicarboxylic acids or alicyclic diols have been known asexcellent in physical and chemical properties, e.g. transparency, heatresistance, chemical resistance, dimensional stability, etc. Suchproperties due to the alicyclic skeleton allow the polyesters to be usedas polymer components for optical materials, structural materials or thelike, such as optical disks, optical cards, or liquid crystal displaycomponents.

There are known various alicyclic bifunctional compounds useful asmonomers for polyesters having an alicyclic skeleton. For example,Japanese Unexamined Patent Publications Nos. 200,830/1991, 5,026/1993and 17,560/1993, etc. disclose alicyclic diol compounds such as bicyclo2. 2. 1!heptane-2,3-dimethanol, tetracyclo 4. 4. 0. 1²,5 . 1⁷,10!-3,4-dimethanol, hexacyclo 6. 6. 1. 1³,6 . 1³,6. 0²,7. 0⁹,14!heptadecane-4,5-dimethanol, etc., alicyclic dicarboxylic acids such asbicyclo 2. 2. 1!heptane-2,3-dicarboxylic acid, tetracyclo 4. 4. 0. 1²,5. 1⁷, 10 !-3,4-dicarboxylic acid, hexacyclo 6. 6. 1. 1³, 6. 1¹⁰, 13.0²,7. 0⁹,14 !heptadecane-4,5-dicarboxylic acid, etc. and diestersthereof.

However, said known alicyclic bifunctional compounds have drawbacks.These alicyclic compounds, in any case of the diol compounds or thedicarboxylic acid compounds, have two functional groups on vicinalcarbons of their alicyclic skeleton. Such neighboring relationship ofthe two functional groups obviously causes steric hindrance, thus makingit difficult to produce a polymer having a higher molecular weight dueto the low reactivity of the monomer. Consequently, the obtainedpolyesters contain considerable amounts of low molecular weightcondensates and show a wide distribution of molecular weight, posing aproblem that the polyester fails to exhibit its inherent properties,such as heat resistance, moisture resistance and chemical resistance, toa full extent although excellent in transparency and mechanicalproperties.

An object of the present invention is to provide novel alicyclicbifunctional compounds free of said drawbacks of known alicyclicbifunctional compounds, and processes for preparing the novel compounds.

Other objects and features of the invention will become more apparentfrom the following description.

The alicyclic bifunctional compounds of the present invention arerepresented by the formula ##STR2## wherein R is a carboxyl group, alower alkoxycarbonyl group or a hydroxymethyl group and n is 0 or 1.

The foregoing compounds of the invention include alicycliccis-dicarboxylic acid represented by the formula ##STR3## and alicyclictrans-dicarboxylic acid represented by the formula ##STR4##

The compounds of the present invention further include alicycliccis-dicarboxylic diesters represented by the formula ##STR5## wherein R'is a lower alkyl group having 1 to 4 carbon atoms, and alicyclictrans-dicarboxylic diesters represented by the formula ##STR6## whereinR' is as defined above.

The compounds of the present invention also include alicyclic cis-diolsrepresented by the formula ##STR7## wherein n is as defined above, andalicyclic trans-diols represented by the formula ##STR8## wherein n isas defined above.

Examples of the lower alkyl group of 1 to 4 carbon atoms represented byR' in the invention are methyl, ethyl, n-propyl, iso-propyl, n-butyl,sec-butyl, tert-butyl, etc. Examples of the lower alkoxycarbonyl grouprepresented by R include carboxyl groups esterified with said loweralkyl group.

The alicyclic bifunctional compounds of the formula (1) of the presentinvention can be prepared from a starting compound, i.e. an alicyclicmonoolefin represented by the formula ##STR9## wherein n is as definedabove, for example, according to the following reaction scheme.##STR10##

In the foregoing reaction scheme, n and R' are as defined above.

The alicyclic cis-dicarboxylic acids of the formula (2) can be preparedby subjecting the double bond of alicyclic monoolefin of the formula (8)(wherein n is 1) to oxidative-cleavage reaction.

The alicyclic trans-dicarboxylic acids of the formula (3) can beprepared by isomerizing the alicyclic cis-dicarboxylic diester of theformula (4) into a trans form, and hydrolyzing the trans form.

The alicyclic cis-dicarboxylic diesters of the formula (4) can beprepared by subjecting the double bond of alicyclic monoolefin of theformula (8) (wherein n is 1) to oxidative-cleavage reaction to give acis-dicarboxylic acid, and esterifying the cis-dicarboxylic acid.

The alicyclic trans-dicarboxylic diesters of the formula (5) can beprepared by isomerizing the alicyclic cis-dicarboxylic diester of theformula (4) into a trans form.

The alicyclic cis-diols of the formula (6) can be prepared by subjectingthe double bond of alicyclic monoolefin of the formula (8) tooxidative-cleavage reaction to give a cis-dicarboxylic acid, esterifyingthe cis-dicarboxylic acid into a cis-dicarboxylic diester, and reducingthe diester.

The alicyclic trans-diols of the formula (7) can be prepared bysubjecting the double bond of alicyclic monoolefin of the formula (8) tooxidative-cleavage reaction to give a cis-dicarboxylic acid, esterifyingthe cis-dicarboxylic acid into a cis-dicarboxylic diester, isomerizingthe diester into a trans form and reducing the trans form.

The alicyclic monoolefins of the formula (8) which are used as thestarting compound in the present invention are known compounds, and themonoolefins can be prepared by known processes. Such monoolefins canmost typically be prepared by a Diels-Alder reaction of cyclopentadieneor dicyclopentadiene as a diene with ethylene or norbornene as adienophile. For example, the reaction of cyclopentadiene with norborneneusually gives various Diels-Alder adducts, e.g. a 1:1 adduct, 2:1 adductor 3:1 adduct of the diene and the dienophile. Product selectivity ofthese adducts depends on the reaction conditions such as the molar ratioof the diene and dienophile, reaction temperature, reaction time, etc.Thus, by the choice of proper reaction conditions, the reaction wouldproduce the desired adduct:tetracyclo 4. 4. 0. 1², 5. 1⁷, 10!-3-dodecene (n is 0 in the formula (8); 1:1 adduct) or hexacyclo 6. 6. 1.1³, 6.1¹⁰, 13 . 0²,7 . 0⁹, 14 !-4-heptadecene (n is 1 in the formula(8); 2:1 adduct). The obtained alicyclic monoolefin can be easilyisolated by vacuum distillation or the like.

Conventional methods per se known can be used for the oxidative-cleavagereaction of the double bond of alicyclic monoolefin of the formula (8)to give an alicyclic cis-dicarboxylic acid.

Various processes are known for preparing a dicarboxylic acid byone-step oxidative cleavage of carbon--carbon double bond in thepresence of an oxidizing agent. For example, there are known a processinvolving oxidation under alkaline to neutral conditions using apermanganate (J. Chem. Soc., Perkin. Trans. 1,806 (1973)), a processusing a bichromate (Org. Synth., vol.3, p.449 (1955)), a process using aperiodate in the presence of a ruthenium metal catalyst (J. Org. Chem.,vol.46, p.19 (1981)), a process using nitric acid (Japanese UnexaminedPatent Publication No.190,945/1984), a process using ozone (J. Am. Chem.Soc., vol.81, p.4,273 (1959)), etc. These known processes foroxidative-cleavage reactions can be used as such in preparing thealicyclic cis-dicarboxylic acids of the invention from the alicyclicmonoolefins of the formula (8).

The inventor of the present invention carried out extensive research onsaid oxidative-cleavage reactions and found the following. Thecontemplated alicyclic cis-dicarboxylic acid is produced in low yieldswhen using a permanganate, bichromate or nitric acid as an oxidizingagent, whereas the contemplated acid can be produced in high yields whenusing a periodate or ozone as an oxidizing agent. However, from aviewpoint of commercial manufacture, the use of periodate or ozoneentails the disadvantages of necessitating cumbersome reaction work-up,requiring expensive reagents, etc.

The inventor carried out further investigations on the foregoingoxidative-cleavage reactions and discovered that when theoxidative-cleavage reaction is effected under acidic conditions using apermanganate as an oxidizing agent, the contemplated alicycliccis-dicarboxylic acid can be produced in a high yield. Whileconventional oxidative-cleavage reactions have been performed underalkaline to neutral conditions, the inventor's proposed oxidativecleavage reaction is carried out under acidic conditions under which theoxidizing ability of a permanganate is enhanced. The proposedoxidative-cleavage reaction will be described below.

Potassium permanganate is desirable among permanganates useful as anoxidizing agent. The amount of the permanganate used is at least 1 moleequivalent, preferably 2 to 4 mole equivalents, per mole of thealicyclic monoolefin of the formula (8).

Usually sulfuric acid, hydrochloric acid, acetic acid, nitric acid andlike inorganic or organic acids can be used to bring the reaction systemto acidic conditions. Among these acids, sulfuric acid, hydrochloricacid and like inorganic acids are desirable since these acids lead tothe decrease in the amount of decomposition products formed asby-products, and they are inexpensive. These acids may be used asdiluted with water, namely in the form of an aqueous solution or may beused as such without dilution. The amount of the acid used is about 0.2to about 3 mole equivalents, preferably about 0.4 to about 2 moleequivalents, per mole of the alicyclic monoolefin of the formula (8). Ifless than 0.2 mole equivalent of the acid is used, the contemplatedproduct is produced in a lower yield, whereas if more than 3 moleequivalents is used, decomposition products are formed as by-productsdue to the acid. Hence the use of the acid in an amount outside saidrange is undesirable.

Solvents useful in the oxidative-cleavage reaction are not specificallylimited insofar as they are inert to the reaction. Useful solventsinclude, for example, water, acetone; tetrahydrofuran, dioxane and likeethers; benzene, toluene, xylene and like aromatic hydrocarbons; hexane,heptane and like aliphatic hydrocarbons; methyl chloride,dichloromethane, chloroform and like halogenated hydrocarbons; etc.Among these solvents, it is desirable, in view of the solubility of thealicyclic monoolefin of the formula (8) and permanganate, to use amixture of water and an organic solvent in an amount of at least onepart by weight per part by weight of the alicyclic monoolefin of theformula (8). More preferably, a water-acetone mixture in a ratio byweight of 1:9-9:1 is used in an amount of at least 3 parts by weight perpart by weight of the alicyclic monoolefin of the formula (8).

In the aforesaid oxidative-cleavage reaction, the alicyclic monoolefinof the formula (8), permanganate and acid may be charged in a lumptogether with the solvent and reacted. Or the reaction may proceed whilethese components are continuously or intermittently charged for thereaction. Other orders of charging are possible. For example, only thepermanganate may be dissolved or suspended in the solvent first, and thealicyclic monoolefin of the formula (8) and acid may be continuously orintermittently added to the reaction system. Or only the alicyclicmonoolefin of the formula (8) may be dissolved or suspended in thesolvent first, and the permanganate and acid may be continuously orintermittently added to the reaction system. Reversely, the alicyclicmonoolefin of the formula (8) and acid may be charged first, and thepermanganate may be continuously or intermittently added to the reactionsystem, or the permanganate and acid may be charged first, and thealicyclic monoolefin of the formula (8) may be continuously orintermittently added to the reaction system. As a further alternative,the alicyclic monoolefin of the formula (8) and permanganate may besupplied first, and the acid may be continuously or intermittently addedto the reaction system.

The temperature for the oxidative-cleavage reaction is in the range ofabout -20° to about 100° C., preferably 0° to about 40° C. The reactiontime is variable depending on the molar ratio of the alicyclicmonoolefin of the formula (8) to a permanganate and on the reactiontemperature, but is usually in the range of about 2 to about 24 hours.

The alicyclic cis-dicarboxylic acid prepared by said oxidative-cleavagereaction is esterified into an alicyclic cis-dicarboxylic diester.

The esterification can be conducted in the conventional manner. Forexample, the esterification is easily carried out by one of thefollowing procedures: (i) using a lower alcohol in the presence of anacid catalyst, (ii) converting the cis-dicarboxylic acid to adicarboxylic acid salt, followed by esterification with a lower alkylhalide, (iii) converting the cis-dicarboxylic acid to an acid halide,followed by esterification with a lower alcohol, and (iv) using a loweralkyl diazo compound such as diazomethane.

Among the above procedures, the procedure using a lower alcohol in thepresence of an acid catalyst is preferred from a commercial viewpoint.Stated more specifically, this procedure comprises esterifying thealicyclic cis-dicarboxylic acid with a monohydric alcohol having 1 to 4carbon atoms in the presence of an acid catalyst such asp-toluenesulfonic acid, sulfuric acid or the like. Examples of themonohydric alcohol are methanol, ethanol, n-propanol, iso-propanol,n-butanol, sec-butanol, tert-butanol, etc. It is suitable to conduct theesterification in the monohydric alcohol. In this case, a preferredamount of monohydric alcohol used is at least 3 times the weight of thealicyclic cis-dicarboxylic acid.

The alicyclic cis-dicarboxylic diester obtained by the esterificationreaction is reduced to an alicyclic cis-diol compound.

The reduction can be easily conducted in the conventional manner byreducing the lower alkoxycarbonyl group to a hydroxymethyl group. Arecommendable reduction is effected, for example, through catalytichydrogenation, or using a metallic hydride compound such as NABH₄,LiAlH₄, etc., or using a metal such as Li, Na, etc.

Among said procedures, the catalytic hydrogenation is preferred in viewof commercial manufacture.

The catalytic hydrogenation can be performed by reducing the alicycliccis-dicarboxylic diester with hydrogen gas in the presence of ahydrogenation catalyst. Useful hydrogenation catalysts include, forexample, copper-chromite, palladium-tin, rhodium-tin, ruthenium-tin andpalladium-zinc catalysts. Among them, a copper-chromite catalyst ispreferred.

It is known to use copper-chromite as a catalyst in catalytichydrogenation for reduction from a diester compound to the correspondingdiol compound (Org. React., vol.8, pp.1-27 (1954)). Various grades ofcopper-chromite catalysts are commercially used. Commercially availablecopper-chromite catalysts can be used as such or in combination with ametallic reduction catalyst such as tin, rhodium, molybdenum, palladium,iron, etc. which serves as a promoter.

The amount of the hydrogenation catalyst used is about 0.01 to about 15%by weight based on the alicyclic cis-dicarboxylic diester. A less amountof the catalyst used prolongs the reduction, whereas its excess amounttends to cause a side reaction. Hence the use of catalyst in an amountoutside said range is undesirable from a viewpoint of commercialmanufacture.

The catalytic hydrogenation is usually conducted in a solvent. Usefulsolvents are not specifically limited insofar as they are inert to thereaction. Useful solvents are, for example, benzene, toluene, xylene,cumene and like aromatic hydrocarbons, hexane, heptane, octane and likealiphatic hydrocarbons, alcohol solvents, ether solvents, etc. Theamount of the solvent used is about 0.1 to about 50 parts by weight perpart by weight of the alicyclic cis-dicarboxylic diester.

An ambient or higher pressure is employed as a hydrogen pressure in thecatalytic hydrogenation. A suitable hydrogen pressure is usually 10kg/cm² or higher. When a copper-chromite catalyst is used, the hydrogenpressure is preferably 100 kg/cm² or higher, more preferably 200 kg/cm²or higher. A lower pressure than said range defers the progress ofcatalytic hydrogenation and is disadvantageous from a viewpoint ofcommercial manufacture. The reaction is accelerated with an increase oftemperature, and this is advantageous from a viewpoint of commercialmanufacture insofar as a side reaction is not involved at an increasedtemperature. A suitable reaction temperature is in the range of about100° to about 300° C., preferably about 170° to about 300° C. Thereactor is not critical insofar as it is a pressure reactorconventionally used for catalytic hydrogenation.

The alicyclic cis-dicarboxylic diester obtained by the foregoingesterification is isomerized to bring the two ester groups into a transconfiguration relation with each other, whereby an alicyclictrans-dicarboxylic diester is produced.

The isomerization reaction is carried out preferably in a manner tocause a metal alkoxide as a catalyst to act on the alicycliccis-dicarboxylic diester.

In this case, an isomerization occurs with ease and in a high yield dueto the catalytic effect of a metal alkoxide used. Generally a carbonylcompound having hydrogen in the α-position of carbonyl group is known tohave a keto-enol type equilibrium in the presence of a basic catalyst.The above-mentioned isomerization reaction was devised by theapplication of this characteristic. A metal alkoxide has not beenconventionally used for cis-trans isomerization of a substituent diestergroup on a polycyclic aliphatic compound. Such isomerization wasdiscovered for the first time by the present inventor.

The present inventor conducted experiments using, as a catalyst forisomerization reaction, alkali metal hydroxides such as sodiumhydroxide, potassium hydroxide, etc., alkali metal amides such aslithium diisopropyl amide (LDA), etc. However, their use resulted in alower isomerization yield than when said alkoxide catalysts were used,or in a side reaction. That is, good results were not obtained.

Examples of metal alkoxides which can be used as a catalyst in saidisomerization reaction are methoxide, ethoxide, n-propoxide,iso-propoxide, n-butoxide, sec-butoxide, tert-butoxide and pentoxide ofalkali metals such as lithium, sodium, potassium and the like. Thesemetal alkoxides may be prepared separately for this purpose or may beprepared in the same system for the isomerization reaction. In the caseof preparing a metal alkoxide in the reaction system, for instance analcohol is reacted with an alkali metal or alkali metal hydride in thesolvent used in the isomerization reaction or in a solvent inert to thereaction, and the resulting solution is used as such in the reaction.These metal alkoxides may be used singly or in mixture with each other.The amount of the catalyst used is not specifically limited, butpreferably in the range of about 0.05 mole to about 0.5 mole equivalent,per mole of the alicyclic cis-dicarboxylic diester. If the amount of thecatalyst is less than 0.05 mole equivalent, an isomerization would notoccur or would proceed at an extremely low rate. Hence it isunpractical. On the other hand, the amount of more than 0.5 moleequivalent would entail a risk of various side reactions concurring.Hence it is undesirable.

While said isomerization is feasible in the absence of a solvent, asuitable solvent is preferably used. Solvents for use herein are notcritical insofar as they are capable of partially or completelydissolving the alicyclic trans-dicarboxylic diester and they are inertto the reaction. Examples of such solvents are organic solventsincluding ethers such as diethyl ether, tetrahydrofuran, dioxane, etc.;aromatic hydrocarbons such as benzene, toluene, xylene, etc.; aliphatichydrocarbons such as hexane, heptane, etc.; alcohols such as methanol,ethanol, etc. Preferred are aprotic organic solvents such astetrahydrofuran, dioxane and like ethers. These solvents which arecommercially available can be used as such to achieve fully satisfactoryresults, and those purified by distillation are more desirable.

The temperature for the isomerization reaction is in the range of about-50° to about 100° C., preferably about -10° to 50° C. A reaction timeof 5 hours or less is sufficient in most cases because the isomerizationquickly proceeds under the above-specified conditions.

The alicyclic trans-dicarboxylic diester obtained by said isomerizationreaction can be converted to an alicyclic trans-diol by being reducedunder the same conditions as in the reduction of the alicycliccis-dicarboxylic diester.

An alicyclic trans-dicarboxylic acid can be produced by hydrolyzing inthe conventional manner the alicyclic trans-dicarboxylic diesterobtained by said isomerization reaction. The hydrolysis can be easilyconducted in the presence of either an acid catalyst or an alkalicatalyst commonly employed. Useful acid catalysts include, for example,hydrochloric acid, sulfuric acid, etc. Useful alkali catalysts are, forexample, sodium hydroxide, potassium hydroxide, etc.

In this way, the alicyclic bifunctional compounds of the formula (1)according to the invention can be prepared.

According to the present invention, there are provided novel alicyclicbifunctional compounds and processes for preparing the compounds. Suchalicyclic bifunctional compounds of the invention are useful asmaterials for polyesters, polycarbonates, etc. Since two functionalgroups in the alicyclic compounds of the invention are not on vicinalcarbons of the alicyclic skeleton, the compound of the invention, whenused as a material for a polyester having an alicyclic skeleton, wouldbe unlikely to cause steric hindrance and can be easily made into apolymer having a higher molecular weight. Because a cis form or a transform alone among the compounds of the formula (1) can be selectivelyproduced according to the invention, only the alicyclic skeleton of thecis or trans form can be introduced into a polymer such as a polyester.As a matter of course, the novel compounds of the invention can also beused as a mixture of cis and trans forms.

The present invention will be described below in more detail withreference to the following Examples but is not limited thereto.

EXAMPLE 1

Preparation of pentacyclo 6. 5. 1. 1³,6. 0²,7. 0⁹,13!pentadecane-cis-10,12-dicarboxylic acid (alicyclic cis-dicarboxylicacid of the formula (2))

Acetone (2 l), 700 ml of water, 35.5 ml (0.67 mole) of sulfuric acid,and 302 g (1.91 moles) of potassium permanganate were charged into a 5 lseparable flask equipped with a stirrer, condenser, thermometer anddropping funnel. A 144 g (0.64 mole) quantity of hexacyclo 6. 6. 1.1³,6. 1¹⁰,13. 0²,7. 0⁹,14 !-4-heptadecene-(alicyclic monoolefin of theformula (8) wherein n is 1) was added dropwise with stirring at 10° to15° C. over a period of 1 hour, followed by 24 hours of reaction at roomtemperature. After removal of manganese dioxide formed from the reactionmixture by filtration, the filtrate was concentrated under reducedpressure, giving 151 g of crude crystals of alicyclic cis-dicarboxylicacid of the formula (2). The crystals were recrystallized from a solventmixture of 140 ml of dimethyl sulfoxide (DMSO) and 115 ml of water,giving 125 g of white crystals having a melting point (decomposition) of256 to 258° C. in a yield of 67 mole % (hereinafter simply indicated by%) based on the starting material, i.e. hexacycloheptadecene. It wasconfirmed by ¹ H-NMR, ¹³ C-NMR, IR and elementary analysis that thecrystals were identical with the contemplated alicyclic cis-dicarboxylicacid. The spectrum data are as follows.

¹ H-NMR (DMSO-d₆): 0.89-0.93 (m, 4H), 1.37-1.42 (m, 3H), 1.57 (s, 2H),1.66 (dt, 1H), 1.72 (d, 1H), 2.03 (s, 4H), 2.16 (q, 1H), 2.56 (d, 2H),2.88-2.98 (m, 2H), 12.05 (s, 2H) (ppm)

¹³ C-NMR (DMSO-d₆): 174.05, 49.65, 47.02, 44.06, 43.73, 38.70, 35.63,34.79, 32.57, 30.98 (ppm)

IR (KBr): 2959, 1719, 1687, 1265, 1202 (cm⁻¹)

Elementary analysis (C₁₇ H₂₂ O₄)

Calcd.: C, 70.32; H, 7.64

Found: C, 70.25; H, 7.54

Example 2

The same procedure as in Example 1 was carried out except that the flaskwas charged with acetone, water, and potassium permanganate, first andthen sulfuric acid and hexacyclo 6. 6. 1. 1³,6. 1¹⁰,13. 0²,7. 0⁹,14!-4-heptadecene were added dropwise to the reaction system throughdifferent dropping funnels over a period of 1 hour. Afterrecrystallization, 130 g of white crystals were obtained (yield 70%). Itwas confirmed by ¹ H-NMR, ¹³ C-NMR, IR and elementary analysis that thecrystals were identical with the alicyclic cis-dicarboxylic acid of theformula (2) prepared in Example 1.

Example 3

The same procedure as in Example 1 was conducted except that the amountof sulfuric acid was changed to 18 ml (0.34 mole). Afterrecrystallization, 122 g of white crystals were obtained (yield 66%). Itwas confirmed by ¹ H-NMR, ¹³ C-NMR, IR and elementary analysis that thecrystals were identical with the alicyclic cis-dicarboxylic acid of theformula (2) prepared in Example 1.

Example 4

Preparation of pentacyclo 6. 5. 1. 1³,6. 0²,7. 0⁹,13!pentadecane-cis-10, 12-dimethyl dicarboxylate (alicycliccis-dicarboxylic diester of the formula (4) wherein R' is a methylgroup)

The alicyclic cis-dicarboxylic acid of the formula (2) prepared inExample 1 (375 g, 1.30 moles), 14.5 g (76 mmoles) of p-toluenesulfonicacid and 3.5 l of methanol were charged into a 5 l separable flaskequipped with a stirrer, thermometer and condenser. An esterificationreaction was performed at a methanol-refluxing temperature for 12 hours.After completion of the reaction, the methanol was distilled off underreduced pressure, giving 415 g of a pale yellow powder. The powder wasrecrystallized from methanol, whereby 381 g of white crystals having amelting point of 142° to 143° C. was obtained in a yield of 92%. It wasconfirmed by ¹ H-NMR, ¹³ C-NMR, IR and elementary analysis that thecrystals were identical with the contemplated alicyclic cis-dimethyldicarboxylate. The spectrum data are as follows.

¹ H-NMR (CDCl₃): 0.95 (dd, 2H), 0.97 (d, 1H), 1.03 (d, 1H), 1.42-1.50(m, 2H), 1.57 (bs, 1H), 1.61 (bs, 2H), 1.68 (d, 1H), 1.88 (dt, 1H), 1.96(s, 2H), 2.13 (s, 2H), 2.52 (q, H), 2.69 (d, 2H), 2.95-3.08 (m, 2H),3.72 (s, 6H) (ppm)

¹³ C-NMR (CDCl₃): 173.38, 51.46, 50.18, 47.70, 44.89, 44.33, 39.07,36.05, 35.16, 32.71, 31.35 (ppm)

IR (KBr): 2943, 1735, 1726, 1439, 1381, 1245, 1189, 1150 (cm⁻¹)

Elementary analysis (C₁₉ H₂₆ O₄)

Calcd.: C, 71.67; H, 8.23

Found: C, 71.55; H, 8.33

Example 5

Preparation of pentacyclo 6. 5. 1. 1³,6. 0²,7.0⁹,13!pentadecane-trans-10, 12-dimethyl dicarboxylate (alicyclictrans-dicarboxylic diester of the formula (5) wherein R' is a methylgroup)

The alicyclic cis-dimethyl dicarboxylate (274 g, 0.86 mole) prepared inExample 4, 1 l of tetrahydrofuran and 19.3 g (0.17 mole) of potassiumtert-butoxide were charged into a 2 l separable flask equipped with astirrer, thermometer, dropping funnel and nitrogen gas inlet tube. Themixture was stirred at 0° C. for 2 hours. With the addition of 50 ml ofwater, the reaction mixture was quenched and was concentrated to about300 ml under reduced pressure. The concentrate was subjected tofractional extraction with 1 l of water and 1 l of ethyl acetate. Theobtained organic layer was concentrated under reduced pressure, giving268 g of pale yellow solids. The solids were recrystallized from hexane,giving 255 g of white crystals having a melting point of 52° to 53° C.(yield 93%). It was confirmed by ¹ H-NMR, ¹³ C-NMR, IR and elementaryanalysis that the crystals were identical with the contemplatedalicyclic trans-dimethyl dicarboxylate. The spectrum data are asfollows.

¹ H-NMR (CDCl₃): 0.92 (d, 1H), 0.98 (dd, 2H), 1.10 (d, 1H), 1.32 (d,1H), 1.45 (d, 2H), 1.55 (d, 1H), 1.68 (s, 2H), 1.94 (t, 1H), 2.04-2.12(m, 1H), 2.14 (s, 2H), 2.23 (s, 2H), 2.23-2.35 (m, 2H), 2.49 (d, 2H),3.69 (s, 6H) (ppm)

¹³ C-NMR (CDCl₃): 175.16, 51.68, 49.18, 48.96, 46.85, 45.25, 36.27,35.93, 35.06, 33.90, 31.27 (ppm)

IR (KBr): 2950, 1736, 1726, 1438, 1367, 1251, 1194, 1143 (cm⁻¹)

Elementary analysis (C₁₉ H₂₆ O₄)

Calcd.: C, 71.67; H, 8.23

Found: C, 71.64; H, 8.35

Example 6

The same procedure as in Example 5 was conducted except that the amountof potassium tert-butoxide was changed to 9.7 g (0.09 mole) in Example5. After recrystallization, 248 g of white crystals were obtained (yield91%). It was confirmed by ¹ H-NMR, ¹³ C-NMR, IR and elementary analysisthat the crystals were identical with the alicyclic trans-dimethyldicarboxylate prepared in Example 5.

Example 7

The same procedure as in Example 5 was conducted except that 9.18 g(0.17 mole) of sodium methoxide was used in place of the potassiumtert-butoxide used as a catalyst in Example 5. After recrystallization,248 g of white crystals were obtained (yield 91%). It was confirmed by ¹H-NMR, ¹³ C-NMR, IR and elementary analysis that the crystals wereidentical with the alicyclic trans-dimethyl dicarboxylate prepared inExample 5.

Example 8

Preparation of pentacyclo 6. 5. 1. 1³,6.0²,7.0⁹,13!pentadecane-trans-10,12-dicarboxylic acid (alicyclic trans-dicarboxylicacid of the formula (3))

The alicyclic trans-dimethyl dicarboxylate (51 g, 0.16 mole) prepared inExample 5, 20 g of sodium hydroxide and 500 ml of water were chargedinto a 1 l 4-necked flask equipped with a stirrer, thermometer andcondenser. The mixture was thoroughly stirred at 105° C. for 2 hours.After completion of the reaction, concentrated hydrochloric acid wasadded until a pH of 1 was reached. The precipitated white crystals werefiltered, washed with water and dried, giving 46 g of white crystalshaving a melting point (decomposition) of 240° to 242.5° C. (yield 99%).It was confirmed by ¹ H-NMR, ¹³ C-NMR, IR and elementary analysis thatthe crystals were identical with the contemplated alicyclictrans-dicarboxylic acid of the formula (3). The spectrum data are asfollows.

¹ H-NMR (CDCl₃): 0.87-1.01 (m, 4H), 1.37-1.51 (m, 4H), 1.62 (q, 1H),1.64 (bs, 2H), 1.93 (quin, 1H), 2.05 (s, 2H), 2.12 (s, 2H), 2.17-2.26(m, 2H), 2.32 (d, 2H), 12.08 (s, 2H) (ppm)

¹³ C-NMR (CDCl₃): 175.87, 48.69, 48.51, 46.40, 44.83, 35.89, 35.64,34.64, 33.77, 30.88 (ppm)

IR (KBr): 2944, 1728, 1700, 1278, 1205 (cm⁻¹)

Elementary analysis (C₁₇ H₂₂ O₄)

Calcd.: C, 70.32; H, 7.64

Found: C, 70.25; H, 7.80

Example 9

(i) Preparation of tricyclo 5. 2. 1. 0²,6 !decane-cis-3,5-dimethyldicarboxylate

A 5 l A separable flask equipped with a stirrer, condenser, thermometerand dropping funnel was charged with 2 l of acetone, 700 ml of water,35.5 ml (0.67 mole) of sulfuric acid and 302 g (1.91 moles) of potassiumpermanganate. Added dropwise was 103 g (0.64 mole) of tetracyclo 4. 4.0. 1², 5. 1⁷, 10 !-3-dodecene (alicyclic monoolefin of the formula (8)wherein n is 0) with stirring at 10° to 15° C. over 1 hour. The mixturewas further reacted at room temperature for 24 hours. After removal ofmanganese dioxide formed from the reaction mixture, the filtrate wasconcentrated under reduced pressure, giving 99 g of crude crystals ofalicyclic cis-dicarboxylic acid. The crystals were recrystallized from asolvent mixture of 110 ml of dimethyl sulfoxide (DMSO) and 90 ml ofwater, giving 85 g of white crystals having a melting point of 250° to255° C.

A 5 l separable flask equipped with a stirrer, thermometer and condenserwas charged with 85 g (0.38 mole) of the above-obtained alicycliccis-dicarboxylic acid, 4.3 g (22 mmole) of p-toluenesulfonic acid and850 ml of methanol. The mixture was subjected to esterification reactionat a methanol-refluxing temperature for 12 hours. After completion ofthe reaction, the methanol was distilled off under reduced pressure,giving 95 g of a pale yellow powder. The powder was recrystallized frommethanol, giving 86 g of white crystals having a melting point of 98° to100° C. (yield 53%). It was confirmed by ¹ H-NMR, ¹³ C-NMR, IR andelementary analysis that the crystals were identical with thecontemplated tricyclo 5. 2. 1. 0², 6 !decane-cis-3,5-dimethyldicarboxylate.

(ii) Preparation of tricyclo 5. 2. 1. 0², 6 !decane-cis-3,5-dimethanol(alicyclic cis-diol of the formula (6) wherein n is 0)

A 300 ml autoclave equipped with an electromagnetic stirrer was chargedwith 30 g (0.12 mole) of thetricyclo 5. 2. 1. 0²,6!decane-cis-3,5-dimethyl dicarboxylate prepared above in (i), 150 ml ofdioxane and 0.5 g of a copper-chromite catalyst. The system was fullyreplaced with hydrogen gas and was further supplied with hydrogen gas toa pressure of 200 kg/cm². Reduction was effected with stirring at 200°C. for 20 hours. After completion of the reaction, the system was cooledto 60° C. or lower, the catalyst was filtered off and the dioxane wasdistilled off under reduced pressure. The obtained pale yellow powderwas recrystillized from a methanol-ethyl acetate solvent mixture,producing 19.8 g of white crystals with a melting point of 115° to 117°C. (yield 85%). It was confirmed by ¹ H-NMR, ¹³ C-NMR, IR and elementaryanalysis that the crystals were identical with the contemplated tricyclo5. 2. 1. 0², 6 !decane-cis-3,5-dimethanol. The spectrum data are asfollows.

¹ H-NMR (CDCl₃): 0.96 (q, 1H), 1.04 (dt, 1H), 1.09 (dd, 2H), 1.21 (dt,1H), 1.36-1.48 (m, 4H), 1.82 (dt, 1H), 2.11 (dt, 2H), 2.23 (bs, 2H),2.22-2.36 (m, 2H), 3.67 (bt, 2H), 3.76 (bt, 2H) (ppm)

¹³ C-NMR (CDCl₃): 61.75, 49.48, 44.97, 36.27, 35.26, 29.32 (ppm)

IR (KBr): 3268, 2946, 2868, 1479, 1458, 1082, 1037, 1012 (cm⁻¹)

Elementary analysis (C₁₂ H₂₀ O₂)

Calcd.: C, 73.43; H, 10.27

Found: C, 73.18; H, 10.39

Example 10

(i) Preparation of tricyclo 5. 2. 1. 0²,6 !decane-trans-3,5-dimethyldicarboxylate

A 500 ml, 4-necked flask equipped with a stirrer, thermometer, droppingfunnel and nitrogen gas inlet tube was charged with 55.0 g (0.218 mole)of the tricyclo 5. 2. 1. 0²,6 !decane-cis-3,5-dimethyl dicarboxylateprepared in Example 9 (i), 300 ml of tetrahydrofuran and 4.80 g (0.043mole) of potassium tert-butoxide. The mixture was stirred at 0° C. for 2hours. With the addition of 20 ml of water, the reaction mixture wasquenched and was concentrated to about 100 ml under reduced pressure.The concentrate was subjected to fractional extraction with 300 ml ofwater and 300 ml of ethyl acetate. The obtained organic layer was washedwith water and concentrated under reduced pressure, giving 54 g of paleyellow solids. The solids were recrystallized from methanol, giving 49 gof white crystals having a melting point of 57° to 59° C. (yield 89%).It was confirmed by ¹ H-NMR, ¹³ C-NMR, IR and elementary analysis thatthe crystals were identical with the contemplated tricyclo 5. 2. 1. 0²,6!decane-trans-3,5-dimethyl dicarboxylate.

(ii) Preparation of tricyclo 5. 2. 1. 0²,6 !decane-trans-3,5-dimethanol(alicyclic trans-diol of the formula (7) wherein n is 0)

A 300 ml autoclave equipped with an electromagnetic stirrer was chargedwith 30 g (0.12 mole) of the tricyclo 5. 2. 1. 0²,6!decane-trans-3,5-dimethyl dicarboxylate prepared above in Example 10(i), 150 ml of dioxane and 0.5 g of a copper-chromite catalyst. Thesystem was fully replaced with hydrogen gas and was further suppliedwith hydrogen gas to a pressure of 200 kg/cm². Reduction was effectedwith stirring at 200° C. for 20 hours. After completion of the reaction,the system was cooled to 60° C. or lower, the catalyst was filtered offand the dioxane was distilled off under reduced pressure. The obtainedpale yellow powder was recrystallized from a methanol-ethyl acetatesolvent mixture, producing 18.5 g of white crystals with a melting pointof 125° to 130° C. (yield 79%). It was confirmed by ¹ H-NMR, ¹³ C-NMR,IR and elementary analysis that the crystals were identical with thecontemplated tricyclo 5. 2. 1. 0²,6 !decane-trans-3,5-dimethanol. Thespectrum data are as follows.

¹ H-NMR (CDCl₃): 0.75 (q, 1H), 0.91 (d, 1H), 0.98 (dd, 2H), 1.32 (d,1H), 1.40-1.49 (m, 4H), 1.42 (s, 2H), 1.65-1.71 (m, 1H), 1.98 (s, 2H),3.29-3.43 (m, 4H), 4.35 (t, 2H) (ppm)

¹³ C-NMR (CDCl₃): 65.07, 51.29, 47.52, 39.53, 34.50, 32.82, 28.27 (ppm)

IR (KBr): 3316, 2929, 2873, 1476, 1452, 1091, 1056, 1013 (cm⁻¹)

Elementary analysis (C₁₂ H₂₀ O₂)

Calcd.: C, 73.43; H, 10.27

Found: C, 73.28; H, 10.33

Example 11

Preparation of pentacyclo 6. 5. 1. 1³,6. 0²,7. 0⁹, 13!pentadecane-cis-10, 12-dimethanol (alicyclic cis-diol of the formula(6) wherein n is 1)

A 300 ml autoclave equipped with an electromagnetic stirrer was chargedwith 38.2 g (0.120 mole) of the pentacyclo 6. 5. 1. 1³, 6. 0²,7.0⁹, 13!pentadecane-cis-10, 12-dimethyl dicarboxylate prepared in Example 4,150 ml of dioxane and 0.5 g of a copper-chromite catalyst. The systemwas fully replaced with hydrogen gas and was further supplied withhydrogen gas to a pressure of 200 kg/cm². Reduction was effected withstirring at 200° C. for 20 hours. After completion of the reaction, thesystem was cooled to 60° C. or lower, the catalyst was filtered off andthe dioxane was distilled off under reduced pressure. The obtained paleyellow powder was recrystallized from hexane, producing 22.3 g of whitecrystals with a melting point of 73° to 77° C. (yield 71%). It wasconfirmed by ¹ H-NMR, ¹³ C-NMR, IR and elementary analysis that thecrystals were identical with the contemplated pentacyclo 6. 5. 1. 1³, 6.0², 7. 0⁹, 13 !pentadecane-cis-10, 12-dimethanol. The spectrum data areas follows. ¹ H-NMR (CDCl₃): 0.90-1.03 (m, 4H), 1.07 (d, 1H), 1.23 (d,1H), 1.41-1.49 (m, 2H), 1.62 (s, 2H), 1.75-1.93 (m, 4H), 2.09 (bs, 2H),2.25-2.38 (m, 2H), 2.25 (bs, 2H), 2.45 (d, 2H), 3.61 (dd, 2H), 3.71 (dd,2H) (ppm)

¹³ C-NMR (CDCl₃): 61.62, 50.12, 44.55, 43.51, 41.33, 39.69, 36.68,35.79, 31.18 (ppm)

IR (KBr): 3293, 2947, 2875, 1484, 1457, 1017, 903 (cm⁻¹)

Elementary analysis (C₁₇ H₂₆ O₂)

Calcd.: C, 77.82; H, 9.99

Found: C, 77.85; H, 10.11

Example 12

Preparation of pentacyclo 6. 5. 1. 1³,6. 0²,7. 0⁹,13!pentadecane-trans-10,12-dimethanol (alicyclic trans-diol of the formula(7) wherein n is 1)

A 300 ml autoclave equipped with an electromagnetic stirrer was chargedwith 38.2 g (0.120 mole) of the pentacyclo 6. 5. 1. 1³, 6. 0², 7.0⁹, 13!pentadecane-trans-10, 12-dimethyl dicarboxylate prepared in Example 5,150 ml of dioxane and 0.5 g of a copper-chromite catalyst. The systemwas fully replaced with hydrogen gas and was further supplied withhydrogen gas to a pressure of 200 kg/cm². Reduction was effected withstirring at 200° C. for 20 hours. After completion of the reaction, thesystem was cooled to 60° C. or lower, the catalyst was filtered off andthe dioxane was distilled off under reduced pressure. The obtained paleyellow powder was recrystallized from hexane, producing 23.5 g of whitecrystals with a melting point of 114° to 115° C. (yield 75%). It wasconfirmed by ¹ H-NMR, ¹³ C-NMR, IR and elementary analysis that thecrystals were identical with the contemplated pentacyclo 6. 5. 1. 1³, 6.0², 7. 0⁹, 13 !pentadecane-trans-10, 12-dimethanol. The spectrum dataare as follows.

¹ H-NMR (CDCl₃): 0.83 (q, 1H), 0.91 (d, 1H), 0.98 (dd, 2H), 1.04 (d,1H), 1.38 (d, 2H), 1.44 (d, 2H), 1.57 (d, 1H), 1.62-1.72 (m, 3H), 1.66(bs, 2H), 1.84-1.93 (m, 3H), 2.10 (d, 4H), 3.52-3.68 (m, 4H) (ppm)

¹³ C-NMR (CDCl₃): 67.18, 49.22, 47.77, 45.81, 45.29, 36.84, 36.46,35.07, 34.17, 31.36 (ppm)

IR (KBr): 3316, 2947, 2925, 2886, 2868, 1481, 1458, 1040, 903 (cm⁻¹)

Elementary analysis (C₁₇ H₂₆ O₂)

Calcd.: C, 77.82; H, 9.99

Found: C, 77.75; H, 10.08

What we claim is:
 1. An alicyclic bifunctional compound represented bythe formula ##STR11## wherein R is a carboxyl group, a loweralkoxycarbonyl group or a hydroxymethyl group and n is
 1. 2. Thecompound according to claim 1 which is an alicyclic cis-dicarboxylicacid represented by the formula ##STR12##
 3. The compound according toclaim 1 which is an alicyclic trans-dicarboxylic acid represented by theformula ##STR13##
 4. The compound according to claim 1 which is analicyclic cis-dicarboxylic diester represented by the formula ##STR14##wherein R' is a lower alkyl group having 1 to 4 carbon atoms.
 5. Thecompound according to claim 1 which is an alicyclic trans-dicarboxylicdiester represented by the formula ##STR15## wherein R' is a lower alkylgroup having 1 to 4 carbon atoms.
 6. The compound according to claim 1which is an alicyclic cis-diol represented by the formula ##STR16##wherein n is
 1. 7. The compound according to claim 1 which is analicyclic trans-diol represented by the formula ##STR17## wherein n is1.